Production of fluoroacetonitrile



H. S. HALBEDEL ET AL PRODUCTION OF FLUOROACETONITRILE Filed March 25, 1946 INVENTOR.

Patented May 25, 1948 UNITED t PRODUCTION F FLUOROACETONITRILE Application March 23, 1946, Serial No. 656,749

3 Claims.

This invention relates to a, method for producing monoiiuoroacetonitrile from monochloroacetonitrile.

We are aware that luoroacetonitrile has been prepared by Swarts (Bull. Soc. Chim. Belg. 31, 364 (1922)) and accordingly we do not make any claim to novelty for the compound itself but only for the nove1 process for producing it. Swarts dehydrated iluoroacetamide to form fiuoroaceton nitrile, whereas we proposed to utilize the fluoroacetonitrile as an intermediate for the production of fluoroacetic acid, its esters, salts, amides etc.

W e have discovered that fluoroacetonitrile can be prepared by the interaction of chloroacetonitrile with a suitable metal fluoride such as silver iiuoride (AgF), mercury fluoride (HgF2) or cadmium fluoride (CdFz) Of these we prefer silver fluoride. 'Ihe reaction may be carried out with the chloroacetonitrile in either the liquid or the vapor state. Chloroacetonitrile can be prepared by catalytic chlorination of acetonitrile, however the source of chloroacetonitrile is immaterial so far as this invention is concerned.

In the accompanying drawings, Fig. 1 is a iiow diagram showing the fluorinating step; Fig. 2 is a flow diagram showing the first step in regenerating the silver uoride (AgF) and Fig. 3 is a iiow diagram showing the second step in regenerating silver uoride.

The reaction between silver fluoride and chloroacetonitrile may be written as follows:

The iiuoroacetonitrile will be mixed with unreacted chloroacetonitrile and may be separated therefrom by fractional distillation since the boiling points of these materials are separated by more than forty degrees. The silver chloride resulting can be regenerated by contact with fluorine which will give AgFz, a. compound which can be reduced to AgF by a suitable reducing agent. In the event mercury uoride (HgFz) is used as the fluorinating agent it can be regenerated from HgClz by treatment with fiuorine. If the iluorinating agent is cadmium fluoride (CdF2) it can be regenerated from CdClz by treatment with HF.

A commercially significant feature of our invention in its preferred embodiment is the fact that the luorinating agent need not be handled but may remain on trays during repeated regenerations while the material to be iiuorinated and the regenerating media in gaseous form are altermately passed over it. Under favorable operating conditions the fluorinating agent may be used and regenerated many times without any handling at (Cl. 2Gb-464) all. If the conditions are allowed to depart too much from the optimum, it may be necessary occasionally to remove the fluorinating agent and crush it to restore its normal powder form.

In Fig. 1 we have indicated the flow diagram for the fluorination of chloroacetonitrile. The fluorinating agent (AgF) is placed ina container T which may take the form of a tray or a series of trays within an enclosed chamber. The chloroacetonitrile in vapor phase is passed over the fluorinating agent in the container T where a portion thereof is converted to iiuoroacetonitrile. The mixture of vapors of chloroacetonitrile and fluoroacetonitrile is separated out by fractional distillation and the chloroacetontrile is returned to the fluorinating chamber T. In the fluorinating chamber meanwhile, the AgF is being converted to AgCl. When this has progressedptor a point that the yield of fluoroacetonitrile is 'uneconomic, the ow of gases is stopped and the fiuorinating agent is regenerated. The first step in the regeneration is accomplished (see Fig.,2) by passing uorine over the material in the container T which at the beginning of the regeneration consists of a mixture of AgF and AgCl, mostly AgCl. After the fiuorine ow has been continued long enough to convert most if not all the AgCl to AgFz, the iiow of fluorine is stopped and CH4 or other suitable reducing agent is passed over the mixture of AgFz, AgF and AgCl in the container T (see Fig. 3) whereby the AgFz is converted to AgF. The uorinating agent is then ready for further use for fluorinating additional quantities of chloroacetonitrile. l

While we prefer to operate according to the method just described, we may use mercury fluoride or cadmium fluoride as the fluorinating agent. If mercury fluoride isused, the regeneration requires only one step, viz., passing fluorine over the mercury chloride-mercury iiuoride mixture in the trays. likewise in the case of cadmium fluoride, only one regeneration step is required, viZ., passing anhydrous hydrogen uoride over the cadmium chloride-cadmium fluoride The reaction may 'be carried out in the liquid Y phase if desired. In this case, a mixture of AgF and ClC-zCN may be reuxed together with vigorous stirring until there is no further lowering of temperature. The liquid phase may then The following examples willserve to illustrateV the invention:

Example I Three hundred parts by weight of monochloroacetonitrile were passed over a bed of 310 parts by weight of nely divided AgF, the vapors being recycled several times. 'Ihe temperature of the bed of AgF was maintained between 126' C. and* 300 C. at all times. In order to determine Whether thereaction occurred atvtherlower temperatures.. Atemperatures of 135 C., 200 C. and 300 C.weretried out vand -it was foundthat conversion tool;V place'throughout the temperature range. We Vconcluded. that anyof these temperaturescould beused with practicable results. The vapors were condensed and fractionated between passes at the'diffe'rent temperatures .to determine whether further reaction had occurred. After the iinalpassage, the total `condensatesr were fractionated,yielding 38 .partsby weight of iluoroacetonitrile,v boiling point 80 C.to 84 C. The mixtureof AgF and AgCl in the bed was regenerated by passing -fiuorine over it until there was no furtherevolution 'of chlorine after which -methane was passed over it Auntilthere was no further evolution of HF. The rbed of Agli was then vused for iiuorination of a further quantityof chloroacetonitrile.

' Example II 128Aparts of silveruoride, AgFand 150 parts of chloroacetonitrile .wereallowed to reflux with vigorous stirring. The initial reiiux temperature was 125 C. At the end vof .40.minutes the temperature haddropped to 103 C. No further loweringsof temperature yoccurred over a period of fifteen minutes and the stirring and heating. was discontinued. The liquid Vwasdecanted and fractionally distilled. 19.0 parts of uoroacetonitrile boiling at 80 C.-85 C. were co11ected.

Having thus described our invention, what we claim is:

1. In a process for preparing monofluoroacetonitrile, the step of passing monochloroacetonitrile in vapor phase over a mass of argentous fluoride.

2. In a process for preparation of monouoroacetonitrile, the step of passing monochloroacetonitrile in vapor phase overa mass of nely divided argentous fluoride maintained at temperatures between the boiling point of monochloroacetonitrile .and 300.C.

3. In aprocess for preparation of monouoro acetonitrile, the steps of passing monochloroacetcnitrile over a bed of finely divided argentous fluoride Vmaintained at a temperature between 126 C. and 300 C. and converting the resulting AgCl in said bed back to AgF by passing sequentially iiuorine and a gaseous carbonaceous reducing agent over said bed.

HAROLD S. HALBEDEL. SAMUEL Z. CARDON. WTLBURJ. SHENK.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,192,143 Midgley et al Feb. 27, 1940 2,403,576 Bradley July 9, 1946 FOREIGN PATENTS Number Country Date 117,464 Australia Sept. 16, 1943 OTHER REFERENCES Moissan,Comptes Rend. (Fr. Acad. Sci), vol. 107, page 1155, (1888).

Swarts, Bull. Soc.Chim.y de -Paris (3), v01. 15, pages 1134-1135 (1896).

Finger et a1.,-Trans. Ill. State Acad. Sci., vol. 29, pages 89-90 (1926). Y

Ruff et al., Zeit. furAnorg. & Allg. Chemie, vol. 219, pages 143-148 (1934).

Simons et al., J. Am. Chem. Soc. vol. 65, pages 2064-2066 (1943).

Simons et al., J. Am. Chem. Soc. vol. 65, pages 389-392 (1943). 

